TW440705B - Optical articles and cathode-ray tube using the same - Google Patents

Abstract

A face panel for a cathode-ray tube is coated with an antireflection film by forming, on the outer surface thereof in this order, a 44.9 nm-thick praseodymium titanate film as a first layer, a 4.9 nm-thick film of a nickel-iron alloy as a second layer, a 53.4 nm-thick praseodymium titanate film as a third layer, a 3.9 nm-thick film of a nickel-iron alloy as a fourth layer, a 20.6 nm-thick praseodymium titanate film as a fifth layer, and an 84.7 nm-thick magnesium fluoride film as a sixth layer. This coated face panel is free from the problem that conventional cathode-ray tube face panels coated on the outer surface with an antireflection film comprising superposed metal films and transparent dielectric films make the cathode-ray tubes exhibit double images although effective in diminishing the reflection of external light on the surface of the cathode-ray tubes and in enhancing display contrast. The cathode-ray tube using the face panel coated with the specific antireflection film does not exhibit double images, is prevented from suffering static buildup on its surface or from reflecting external light thereon, and can attain higher image contrast.

Description

440704S V. Description of the invention (l) The invention of the invention This invention relates to a glass product coated with a film. In the present invention, D: a conductive and light-absorbing anti-reflective glass panel, or a broken glass panel which is bonded to a glass substrate for the background of the invention. In the display using a cathode ray tube, the quality of the display is enhanced, and the imagination is adopted: T is the reflection of light in a television receiver '. Because of this, to reduce the use of high electrons in the display from the surface of the display tube, these cathodes use the 'cause' to attract floating display in the air: the surface of the device is charged with static electricity, and measures are taken in order to Avoid waves from the monitor. In particular, such display electric films are used to shield electromagnetic-layer conductive anti-reflective thin glass plates: they are manufactured and coated; or they are a technology, "the surface of the panel itself, Apply a conductive anti-reflection film directly. In order to strengthen the quality of the cathode-ray tube, the example of # H & a # a ^ & is not added, examples of such glass printing are included in JP-A-6-263483 ("JP- A " is used herein to refer to " unexamined and published Japanese patent application "), with glass plate / ITO / titanate fin / magnesium fluoride / titanate fin / magnesium fluoride,

Multi-layered structure. Example of a conductive anti-reflective thin film including an overlapping layer of metal and transparent oxide. [Page 7 of 88]] 6158, ptd 4407〇4. 15. Description of the invention (2) Child 'includes, in jp — A-64-70 70 The multi-layer structure described in glass plate / metal / titanium oxide / silicon oxide, as disclosed in Jp-1 ^ 80333, glass plate / magnesium fluoride / metal / Titanium oxide / magnesium fluoride, as described in the multilayer structure; and the multilayer described as "glass / rhenium titanate / metal / rhenium titanate / magnesium fluoride" disclosed in Japanese Patent No. 2,565,538 Structure "The metal layer disclosed in these references is composed of stainless steel, titanium complex, stainless steel, stainless steel, alloy, etc." In JP A 1-200952, a multilayer structure with four layers is disclosed, including two A metal layer, such as rhenium, is represented by glass plate / stainless steel / rhenium titanate / stainless steel / magnesium fluoride. In addition, a conductive anti-reflection film formed by superposing a non-metallic light absorbing film and a transparent dielectric film is disclosed in JP_A_9_ 1 5 6 9 64. The multi-layer structure is expressed by glass plate / titanium nitride / silicon nitride / silicon dioxide. The above-mentioned antireflection film composed of-or an overlapping layer of a light-absorbing film and a transparent dielectric film made of a metal or a metal nitride, when directly or indirectly placed on the front surface of a cathode ray tube has been obtained. It can effectively reduce the transmittance and strengthen the display contrast. However, the anti-reflection film disclosed in JP-A-6-263483 is not because: some layers are made of transparent oxides. Therefore, when the anti-radiation film is placed in front of the cathode ray tube, despite its electrical properties and high transmittance, it does not & 纟 # gs', which enhances the contrast and makes the display look beautiful. Have. On the other hand, in the prior art, the conductive anti-reflection film of Baodong Modi * has a transmittance ratio that can be adjusted to allow the Si-oxygen chamber to be laminated with a metal layer thickness.

88116158.ptd Page 8 V. Description of Invention (3) To be controlled. In this way, the value of the transmittance can be specified in the range of 30 to 50%, which is advantageous for enhancing the display contrast. However, these antireflection films have been found to have a problem: when the thickness of the constituent film is adjusted to reduce the reflectance of external light on the outer surface of the antireflection film, the reflection at the interface between the transparent substrate and the antireflection film The ratio will increase. In the cathode ray tube, the high reflectance at the interface between the glass and the antireflection film causes a problem: whether the cathode ray tube uses a glass plate directly coated with the antireflection film, or the cathode ray tube uses a panel, and the Examples of the bonding of glass substrates coated with an anti-reflection film, 'cathode-ray tube displays all show a doub image. In a cathode ray tube, the problem of ghosting is particularly serious when the panel itself has a high internal transmittance. The prior art disclosed in JP-A-9-1 56964, an anti-reflection film composed of an overlapping layer including a metal nitride film and a transparent dielectric film, also has the above problem. The part that accompanies the polar ray tube has a reason to use—disadvantages: the dark image part has internal transmission to the image, and the glass of the plate is coated with a large cathode. For a larger brightness ratio. When the inner ray tube with the thickness of the previous panel is lower than the thickness of the inner ray tube to make the glass thickness, there is no such technology in the surrounding panel which is provided to maintain the transmission of the strong part and it is necessary to make the difference to include the flattening so as to make the degree. As much as possible, the glass part is more mechanical, and the inside of the glass is transparent metal.

Its surrounding part manages the above heavy glass to eliminate the strength of its central part, but the surrounding part itself must have a ratio of the surface or metal nitrogen. Therefore, the problem of using it more than its central shadow can be 'this means that there is a part' Its surrounding and central parts have raised plates at 44 07 0

In the case of an anti-reflection film, the coated plate has a high reflection ratio at the interface between the glass and the anti-reflection film, so that the anti-reflection film has a ghost image. Summary of the invention An object of the present invention is to remove For example, when an anti-reflective film containing a light-absorbing thin film is formed on the outer surface of a cathode ray tube panel, or when a glass plate is coated with an anti-reflective film containing a light-absorbing film, When bonded to a cathode ray tube panel. Another object of the present invention is to avoid the reflection of external light on the display surface and obtain a high display contrast. The present invention provides an optical article with an anti-reflective coating, which Contains a light-transmissive substrate with a refractive index of 1.4 to 1.7, and an anti-reflective film composed of overlapping layers, formed on the light-transmissive substrate in the following order: the light-absorbing film is the first layer of a transparent substrate with a refractive index of 1.6 to 2.4 The electric film is the second layer, the light absorbing film is the third layer, and the transparent dielectric film with the refractive index of 1.6 to 2.4 is the fourth layer, and the transparent dielectric film with the refractive index of 1,35 to 1.5 is the fifth layer. Here, the value of the refractive index refers to a value measured at a wavelength of 55 nm. Examples of the material of the light-absorbing film include metals, alloys, and metal nitrides. The two light-absorbing films are individually sandwiched by the refractive index. .6 to 2.4 are laminated between transparent dielectric films. This specific example is important; it allows light that strikes the anti-reflection film through a light-transmissive substrate to pass through the substrate / anti-reflection film interface. When reflecting, it can have a reduced reflectance. These two light-absorbing films can be made of the same or different materials. The preferred products of this optical product are the transparent dielectric films of the second and fourth layers, The individual thickness is 30 to 80 nm;

88116158.ptd Page 10 '4407 0 I. Description of the invention (5)-The thickness of the transparent dielectric film is 60 to 100 nm. The thickness of the transparent dielectric films as the second and fourth layers, respectively, is preferably 30 nm or more, and more preferably 4 Onm or more; preferably 80 nm or less, and more preferably 60 nm or less ; Its foothold is such that the light incident on the anti-reflection film through the light-transmissive substrate can have a reduced reflectance when reflected at the substrate / anti-reflection interface; therefore, it is determined to avoid the occurrence of ghosting without Error β The thickness of the transparent dielectric film as the fifth layer is preferably 60 nm or more, and more preferably 65 nm or more; more preferably 100 nm or less, and 80 nm or less It is smaller and better; it is based on the fact that the light that is incident on the anti-reflection film through the light-transmissive substrate can have a reduced reflectance when reflected at the substrate / anti-reflection film interface; thus avoiding ghosting and No mistakes. The preferred product of this optical product, wherein the light-absorbing thin film is an element or a thin film of a mixture of two or more elements; the element is made of titanium, chromium, file, molybdenum, iron, niobium, molybdenum, rhenium, nickel , Nickel-iron alloy and stainless steel. The thin film 'of any one of these metals and alloys, or a mixture of two or more, has almost no color and therefore has the characteristics of a transparent thin film; therefore, the color of the color image presented by the cathode ray tube is not impaired. The preferred products of this optical product, wherein the light-absorbing thin layers as the first and third layers, respectively, are composed of metal, and the individual thickness is 5 to 18 nm. A thickness of less than 5 nm is not good. Such an anti-reflection film not only has insufficient light absorption properties to reduce the contrast of the displayed image, but also impairs the antistatic properties. From this standpoint, the thickness of the first and third layers is 6 nm or more

^ 44 07 0 ii

Big better. On the other hand, a thickness exceeding 8 nm is not good. Such an anti-reflection film has too high light absorption properties, which causes the displayed image to become dark. From this standpoint, the thicknesses of the first and third layers are preferably 12 nm or less. The thickness of the individual light absorbing film is selected so that the visible ray transmission ratio of the optical article is better in the range of 30 to 50%. A preferred article of this optical article is a transparent dielectric film having a refractive index of 16 to 24, and at least one layer is a film of chromium oxide. — The preferred product of this optical 2 product, wherein the light-absorbing film is a thin element of one element or a mixture of one or more elements; this element is made of titanium nitride chromium nitride, zirconium nitride, hafnium nitride, And molybdenum nitride selected from the group of metal nitrides. Any of these metal nitride films has almost no color, so it has the characteristics of a transparent 4 film; therefore, it does not damage the color of the color image presented by the cathode ray tube. A better product for school products, where the light absorbing films as the first and third layers, respectively, are composed of metal nitrides, and the individual thickness is 3 to 6ηπ ^ If the thickness is less than 3nm, such antireflection films are not only Its light absorption and biomass are not enough to reduce the contrast of the displayed image, and also damage the antistatic properties. On the other hand, if the thickness exceeds 6 nm, such an anti-reflection film absorbs too much light ' and causes the displayed image to become dark. The thickness of the individual light-absorbing films is selected so that the visible ray transmission ratio of this optical article is better in the range of 3050%. The invention further provides an optical article with an anti-reflection coating, which comprises a light-transmissive substrate having a refractive index of 1′4 to 1.7, and an overlapping layer

4 4 07 0 (4Γ V. Description of the invention (7) Anti-reflection film composed of the following, a transparent dielectric thin layer with an emissivity of 1.6 to 2.4, and a refractive index of 1.6 to 2.4 Four layers, and a refractive index of 1.35 layers are sequentially formed on the light-transmissive substrate: the folded film is the first layer, the light-absorbing film is the second dielectric film is the third layer, and the light-absorbing film is 1.5 transparent dielectric film is Fifth, the refractive index value is a value measured at a wavelength of 55 nm. Examples of the material of the light-absorbing film include metals, alloys, and metal nitrides. The two light-absorbing films are sandwiched by the refractive index individually. 16 to 24 are laminated between transparent dielectric films. This specific example is important; it allows light that is incident on the anti-reflection film through a light-transmissive substrate to be reflected at the substrate / anti-reflection film interface. , Can have a reduced reflectance. These two light-absorbing films are made of the same or different materials. The preferred product of this optical product is a transparent dielectric film with a refractive index 丨. 6 to 2.4 As the sixth layer, interposed between the light-absorbing film as the fourth layer and the fifth layer Between the transparent dielectric films. Preferred products of this optical product, wherein the transparent dielectric films are used as the first and third layers, respectively, each having a thickness of 30 to 80 nm; and the transparent dielectric as the fifth layer. The thickness of the film is 60 to 100 nm. The thicknesses of the transparent dielectric films of the first and third layers, respectively, are preferably 30 nm or more, and more preferably 40 nm or more; nm or less is preferred, and 60 nm or less is more preferred; it is based on the fact that the light incident on the anti-reflection film through the light-transmissive substrate can be reflected at the substrate / anti-reflection film interface. Reduced reflectance; therefore, it is determined to avoid the occurrence of ghosting without errors.

88116158.ptd Page 13

V. Description of the invention (8) The thickness of the transparent dielectric film as the fifth layer is preferably 60 nm or more ', more preferably 65 nm or more, more preferably loonm or less, and more preferably 9 5 nm or more Small is better; its foothold is' to make the light incident on the anti-reflection film through the light-transmissive substrate 'when reflected at the substrate / anti-reflection film interface' have a reduced reflectance; thus avoiding ghosting and No mistakes. The preferred article of this optical article 'is that the thickness of the transparent dielectric thin film as the sixth layer is not more than 100 nm. The thickness of the transparent dielectric film as the sixth layer exceeding 100 nm is not good because it causes too much reflectance. The thickness of the sixth field to obtain a reduced reflectance of the vertical field is preferably 70 nm or less, and more preferably 30 nm or less. The preferred product of this optical product is a light-absorbing film selected from the group consisting of several or two or more elements mixed with a metal group consisting of chromium, cone, molybdenum, iron, niobium, buttons, and rhenium, each of which is an object. This element is a film made of any one of these metals and alloys, such as titanium, nickel, nickel-iron alloys, and stainless steel, or a mixture of two or more, with almost no color, so it has the characteristics of a transparent film; therefore, it does not damage The color of a color image presented by a cathode ray tube. "This is not the preferred product of the optical product, in which the light absorbing film, individual 3 to 6 nm. This is the preferred product of the optical product, in which the refractive index is from 6 to 2.4. At least one layer of the dielectric film is oxidized Chromium film. The light absorbing films are the second and fourth layers, respectively, metal or metal.

5. Description of the invention (9) Alloy thin film 'The thickness of the individual light absorbing film is preferably 3 to 6 nm. An anti-reflection film having a thickness of less than 3 nm is not good. Not only is its light absorption property insufficient to reduce the contrast of the displayed image, but it also impairs the antistatic property. On the other hand, a thickness exceeding 6 nm is not good, and such an anti-reflection film absorbs too much light 'and causes the displayed image to become dark. The thickness of the individual light absorbing films is selected so that the visible ray transmission ratio of this optical article is better in the range of 30 to 50%. A preferred product of this optical product is one of the light-absorbing films, which are each a film or a mixture of two or more devices; the device is made of nitride, nitride, nitride, hafnium nitride, and nitrogen. It is selected from the group of metal nitrides. Any of these thin films of metal nitride 'has almost no color, so it has the characteristics of a transparent film; therefore, the color of the color image presented by the cathode ray tube is not impaired. A preferred article of this optical article, wherein the light-absorbing film has an individual thickness of 5 to 18 nm. The film absorbs too much light, causing the displayed image to become dark. From here

Among them, the light-absorbing films as the second and fourth layers, respectively, are each composed of a metal nitride. The thickness of the individual light-absorbing films is preferably 5 to 8 nm. A thickness of less than 5 nm is not good. Such an anti-reflection film not only has insufficient light absorption properties to reduce the contrast of the displayed image, but also impairs the antistatic properties. From this standpoint, the thickness of the second and fourth layers is preferably 6 nm or more. On the other hand, 'thickness exceeding 18_ is not good, such antireflection. 5. Description of the invention (10) Selection of thickness of light film' so that the visible ray transmittance of this optical product is in the range of 30 to 50%. Better. A preferred article of this optical article, wherein the light-transmitting substrate is a glass substrate. This glass substrate is bonded to the outer surface of the cathode ray tube panel with an adhesive. Since such a panel usually has a slightly curved outer surface, the glass substrate is preferably already curved, so that it can be bonded to the curved surface by an adhesive layer having a uniform thickness. This glass substrate may be a colorless or colored glass plate. The composition of the glass is not particularly limited, and usable examples include a soda lime silicate component, a borosilicate component, an aluminosilicate component, and an aluminoborosilicate component. This glass substrate can be made stronger by air cooling. Generally speaking, float glass with soda lime silicate composition is often used because it is not expensive. A preferred product of this optical product, wherein the light-transmitting substrate is a glass panel for a cathode ray tube. A preferred article of this optical article is one in which the glass contains a colored component and is therefore light absorbing. Glass can contain examples of light-absorbing ions (colored ions), including nickel, iron, cobalt, selenium, thallium, and titanium. Mixing at least one of the above-mentioned ingredients in the glass' gives a light-absorbing transparent glass; for example, gray, green, or bronze colors can be obtained. It is better to use glass with light absorption properties, because this glass can effectively reduce the amount of light reflected at the interface between the glass substrate and the anti-reflection film for light that reaches the anti-reflection film after passing through the glass substrate; it will be described Later. This glass can contain other additions

88116158.ptd on page 16 with 〇 0 70 "'5. Description of the invention (II), such as barium, strontium, antimony, zi and zirconium. The present invention further provides a cathode ray tube using the above glass product. Contains Examples of transparent dielectric films having a refractive index of 1.6 to 2.4 in each optical article of the present invention include hafnium titanate, hafnium oxide, indium oxide, tin-doped indium oxide, and niobium oxide , Titanium oxide, bismuth oxide, oxidized aluminum, rolled group, oxide oxide, nitride oxide, tin oxide, and oxide complex. Examples of transparent dielectric films with a refractive index of 1.35 to 1.5 include Films with fluorinated locks and di-emulsions. These transparent dielectric films can be deposited using conventional techniques, such as, for example, vacuum evaporation, ion bonding, and sputtering. Light-transmissive substrates It can be a flat plate or a plastic film. When a metal film is used as the light absorbing thin film in each optical article of the present invention, at a longer wavelength, the optical article has a lower transmittance 'because In the range 340 to 780nm, metal thin films The longer wavelength has a higher light absorption coefficient than the shorter wavelength. In the transparent dielectric thin films listed above, the chromium oxide film shows a slight absorption in the visible light range; and, for shorter wavelengths, The longer wavelength absorbs a larger amount of light. Therefore, when a metal film is used as a light absorbing film and a chromium oxide film is used as a transparent dielectric film, then this anti-reflective film can be adjusted so that it can be seen in the entire visible range The transmittance is constant or slightly higher at longer wavelengths. In other words, the difference between the two kinds of thin Ϊ 'ί long ί dispersion properties can be used to control how much the spectral J-emission ratio Curve. From this standpoint, it is better to choose a metal film as the light absorbing film and a chromium oxide film as the transparent dielectric film. 88ll6158.ptd Page 17 0 ^ V. Description of the invention (12) Brief description Fig. 1 is a sectional view of a specific example of an optical article according to the present invention. Fig. 2 is a surface view of a specific example of a cathode ray tube according to the present invention. In the specific example of the optical article of the invention, the multilayer structure of the antireflection film. Fig. 4 is a diagram describing the principle of ghosting. Fig. 5 is a diagram describing L, Tint, and q of a glass substrate. Fig. 6 is a diagram describing Figures of the heart, r2, and r3 of the optical article. Figure 7 is a graph showing the internal transmittance Tint and surface reflectance q of the glass substrate used in Example 1. 'Figure 8 The transmission & T2 of the optical article obtained in Example 1 and its surface reflectance r3 on the surface of the antireflection film and its reflectance r2 on the glass substrate / antireflection film interface are shown. Fig. 9 is a spectral graph, respectively The transmittance T2 of the optical article obtained in Example 12 and its surface reflectance ra on the surface of the antireflection film and its reflectance r2 at the glass substrate / antireflection film interface are shown. Description of element number 1: Fluorescent substance 2: Translucent substrate 2a. Glass substrate 2b: Glass panel 3: Anti-reflective film 1 Oa: Optical product using glass substrate of the present invention 10b: Glass substrate of the present invention Optical products

88116158.ptd Page 18 V. Description of the invention (13) 11: The cathode ray tube 1 2 of the present invention · The frit sealing layer 13: the electronic grab unit 14: the funnel-shaped body 31: the refractive index is 1.6 to 2, 4 Transparent dielectric film 32: Light absorbing film 3 3: Detailed description of the invention of a transparent dielectric film having a refractive index of 1.3 to 1.5. FIG. 1 is a cross-sectional view showing a specific example of an optical article according to the present invention. The optical product i0a shown in FIG. 1 (a) includes a glass substrate 2a, and an anti-reflective sheet 3 is deposited on the surface. This optical product is bonded to the panel of the cathode ray tube with an adhesive so that the anti-reflection film faces inward. As described in the sectional view of FIG. 1 (b), another specific example of the optical product according to the present invention includes A glass panel 2b for a cathode ray tube, and an antireflection film 3 are directly deposited on the outer surface of the panel. Fig. 2 is a cathode ray tube of the present invention! Surface view of the specific example. In this specific example, a glass product as shown in FIG. 1 (b) is used. This glass article 10b is coated with a fluorescent substance 1 inside, and is bonded to the funnel-shaped body 14 with a glass frit 12, wherein the electronic grab unit 13 has been fixed. Fig. 3 is a sectional view illustrating an anti-reflection film in a specific example according to the present invention. This specific example includes a light-transmissive substrate 2 with a refractive index of 1> 4 to 17; and a superimposed on its surface in the following order: a transparent dielectric film 31 with a refractive index of 1.6 to 2.4, and a metal film 32 , The transparent dielectric film 31 with a refractive index of 丨. 6 to 2.4, the metal thin film 32, the transparent dielectric film with a refractive index of 丨. 6 to 2.4.

_

5. Description of the invention (14) The film 31 'and the transparent dielectric film 33 having a refractive index of 1.35 to 1.5. FIG. 4 is a diagram optically describing a ghost in a display. FIG. 5 is a diagram describing the internal transmittance Tint of the glass substrate used in the present invention, the reflectance r on the side where it does not have antireflection thin], and its transmittance Figures; these properties are described below. FIG. 6 is a diagram describing the reflection ratio r2 of the light directed to the antireflection film via the glass substrate in the optical article of the present invention, that is, the reflection ratio at the antireflection film / glass interface; A graph of the reflectance & FIG. 7 is a graph showing the spectral properties of the glass plate used in Example 1. FIG. Fig. 8 is a graph showing the spectral properties of the optical article obtained in Example 1. In FIG. 4, light is emitted from the fluorescent substance 1 and passes through the glass substrate 2 a to reach the interface between the glass substrate 2 a and the anti-reflection film 3. Part of the light 4 transmitted through the antireflection film 3 * is considered as an image. However, the remaining part of the light is reflected by the interface between the glass substrate 2a and the antireflection film 3 'to obtain reflected light 5. This reflected light 5 is further reflected by the interface between the glass substrate 2a and the fluorescent substance 1, and a reflected light 6 is obtained. This reflected light 6 passes through the glass substrate 2a and the anti-reflection film 3 and reaches the viewer. The generated transmitted light 7 can be viewed as an image. As a result, the viewer can visually observe two rays, the transmitted light 4 and the transmitted light 7 at the same time. In other words, the viewer observes a double image. The problem of ghosting arises. As the internal transmittance of the glass becomes higher, ghosting becomes more severe. In contrast, in the case where the glass has a low internal transmittance, the reflected light 5 and 6 are absorbed by the glass as it passes through the glass. As a result, the amount of transmitted light 7 is small and cannot be observed by the viewer. In other words, ghosting does not occur.

88116158 ^ 1 (1 page 20 V. Description of the invention (15) The following definitions are applied in this article. (1) Surface reflectance of glass substrate: Γι (2) Transmission of glass substrate: Tj (3) of glass substrate Internal transmittance: Tint (4) Reflectance for optical products incident from the opposite side of the antireflection film: (5) Reflectance for optical products at the glass substrate / antireflection film interface: r2 (6) Coating The surface reflectance of the optical product on one side of the antireflection film: r3 (7) The transmittance of the optical product: T2 As shown in FIG. 6, the optical product of the present invention has a reflectance r2 at the glass substrate / antireflection film interface. Measured in the following way. First, the transmittance of a glass substrate in the form of a plane parallel plate was measured before the formation of the anti-reflection film. Second, one side of the glass substrate was sandblasted to make the surface rough. Coloring (this process is called " anti-reflective treatment "). Light is therefore impinged on the glass substrate by the opposite surface 11 to measure the reflectance. This reflectance is defined as the surface reflectance q, as shown in Figure 5 .Glass-based The measured values of the transmittance T! And surface reflectance Γι are both obtained spectrophotometrically and substituted into equation (1) to calculate the internal transmittance Tint of the glass substrate. Figure 5 shows the internal transmittance Tint of the glass substrate The transmittance 1 of the glass substrate and the surface reflectance r! Of the glass substrate (Equation 1)

Tint = 2V ((U + 〇〇2)

88116158.ptd Page 21 L 44 07 0 * 4 ^ 'V. Description of the invention (16) Furthermore, an anti-reflection film was deposited on a glass substrate having the same optical properties as the glass substrate above, and a sample of the glass product was prepared. ; Examine with the spectral center of the reflectance of the light incident on the glass substrate from the opposite side of the anti-reflective sheet (see Figure 6). Using equation (2), the glass substrate / anti-reflection can be calculated from the reflectance of the glass product on the opposite side of the anti-reflection film, the surface reflectance of the glass substrate, and the internal transmittance of the glass substrate, Tint. The reflection ratio r2 of the optical product at the film interface. (Equation 2) r2 = (R1-r1) / (((Rj-r ^ r ^ Cl-r!) 2) Tint2) The optical method at the glass substrate / anti-reflective film interface by the method described above: reflection of the product The ratio r2 is determined. Fig. 6 shows the reflectance r2 of the optical article at the interface of the glass substrate / antireflection film, and the reflectance & of the glass article at the opposite side of the antireflection film. The present invention will be explained in more detail with reference to the following examples and comparative examples, but the present invention should not be construed as being limited to these examples. In the examples and comparative examples, the thin film deposition was processed in the following manner. PrTitanium Titanate (PrTi03) layer: Evaporation is performed using PrTi03 pellets as an evaporation source. Nickel-Iron Alloy (NiFe) Layer: The nickel-iron alloy sheet is used as an evaporation source to vaporize bonds. Magnesium fluoride (MgFz) layer: MgF2 pellets are used as an evaporation source for evaporation. Stainless steel (NiFeCr) layer: a stainless steel sheet is used as an evaporation source for evaporation. Silicon nitride (S i Nx) layer: Uses silicon as a target for reactive sputtering.

88116158.ptd Page 22 4 4 07 0 V. Description of the invention (Π) Titanium nitride (T i Νχ) layer: Use titanium as a target for reactive sputtering. Silicon dioxide (Si 02) layer: using silicon as a target for sputtering. Alumina (A 1203) layer: Use aluminum as a target for sputtering. Example 1 A colored glass plate having dimensions of 100 mm, 100 mm, and 14 mm (thickness) was examined for a surface reflection ratio 1 ^ and a transmission ratio T! In a wavelength range of 340 to 780ητη. The measured values of these transmittances and surface reflectances are substituted into Equation 1 to calculate the internal transmittance Tint of the glass substrate. The wavelength spectrum of internal transmittance and surface reflectance is shown in 圊 7. Next, 'the glass substrate whose internal transmittance and surface reflectance have been determined' is placed in a vacuum evaporation system and heated to 300 ° C with a substrate heater arranged in the evaporation system. When this glass substrate is continuously heated in this way, an antireflection film having a multilayer structure as shown in Table 1 is deposited on this glass substrate. Therefore, a sample 1 of an optical article according to the present invention was manufactured. To vaporize this evaporation source, an electron beam evaporation method is used. The distance between the evaporator and the glass substrate was adjusted to 100cm, and when the glass substrate was returned, the 'deposition was formed' before the individual composition film was deposited 'and the vacuum box was evacuated with an oil diffusion pump to 〇. 〇〇 3 Pa. During the deposition of nickel-iron alloy (NiFe) films, praseodymium titanate (PrTiO3) films (refractive index 2.14), and vaporized ballast (MgF2) films (refractive index 丨 .38), oxygen was not introduced. The obtained optical article was taken out of the evaporation system, and the composition of the NiFe film was determined by chemical analysis. As a result, the nickel / iron ratio was measured to be 81: 19 (by weight). The obtained samples were examined for their transmittances in the wavelength range of 34 to 78 nm and

88116158.ptd Page 23 1 1 1 " ^ V. Description of the invention (18) The reflectance on the opposite side of the antireflection film. These measured values are substituted into Equation 2 to determine the reflectance r2 at the glass substrate / anti-reflective film interface. In addition, the surface reflection ratio r3 of the side opposite to the sample of the antireflection film was uniformly sandblasted and a black oil-based pen was subjected to antireflection treatment, and then the surface coated with the antireflection film was measured. Fig. 8 is a wavelength spectrum showing the transmittance T2, the reflectance r2 at the glass substrate / anti-reflective film interface, and the surface reflectance r3 of the surface coated with the anti-reflective film, which are thus determined. The visible light transmittance Tv, the visible light reflectance r3v on the side coated with the antireflection film, and the visible light reflection & r2v at the glass substrate / antireflection film interface can be obtained from the spectrum shown in FIG. 8 according to JIS R 3 1 06 ( 1 998) (Calculated. The results obtained are shown in Table 2. The outer surface of a cathode ray tube panel having almost the same glass composition as the glass substrate used above was coated under the same film deposition conditions as above. A layer of anti-reflective film. The visible coating transmittance is 35.7% for the entire coating panel produced. This panel is used to make a cathode ray tube 'and the image presented by this cathode ray tube is observed in a dark room. Results The displayed contrast is satisfactory. Since the visible light reflectance at the interface between the panel and the anti-reflection film is as low as 0.19%, ghosting does not occur. Furthermore, even when the cathode ray tube is under fluorescent light When viewed in a room illuminated by a lamp, the surface of the panel is not reflecting fluorescent light because the surface reflectance on the side coated with the anti-reflection film is as low as 0.26%. Like exhibit excellent visibility. In order to make the antireflection film having an antistatic function, the antireflection film is considered to have a sheet resistance 2k Ω / □ or less is preferred. In order for this antireflection film can

88116158.ptd Page 24 44 07 Ο V. Description of the invention (19) Shields electromagnetic waves harmful to the human body emitted by the cathode ray tube, and the anti-reflection film is further considered to have a sheet resistance of 500 Ω / □ or more Low is better. The sheet resistance of Sample 1 of the antireflection film was measured, and the measured values are shown in Table 2. Its sheet resistance is 112Ω / □, which indicates that this anti-reflection film has antistatic function and electromagnetic shielding function. Example 2 The same glass substrate as in Example 1 was coated with an antireflective film having a multilayer structure as shown in Table 1 via vacuum distillation. A thin nickel-iron-chromium alloy thin film, which is used as a light-absorbing film, was determined by chemical analysis. As a result, the ratio of nickel / iron / chromium was measured to be 77.0 / 7.8.15, 2 by weight. The obtained sample of the optical article was examined for its transmittance and reflectance on the opposite side of the antireflection film. From these measured values, the visible light reflection ratio at the glass substrate / anti-reflective film interface was determined in the same manner as in Example 1. In addition, the surface opposite to the sample of the antireflection film was subjected to an antireflection treatment, and then the surface reflectance of the surface coated with the antireflection film was measured. From these measurement results, the visible light transmittance Tv, the visible light reflectance r3v on the coating surface, and the visible light reflectance r2v at the glass substrate / anti-reflective film interface were calculated from J IS R 31 0 6. The results obtained are shown in Table 2. The visible light transmittance of the sample is 35.6%, and its value is advantageous for enhancing the contrast of the display. Because the surface reflectance on the side coated with the anti-reflection film was as low as 0.32%, almost no image reflection occurred on the coated side of the sample. Furthermore, because the reflection ratio is low at the glass substrate / anti-reflective interface

88116158.ptd Page 25 44 07 V. Description of the invention (20) to 0.14%, almost no ghosting is observed. The sheet resistance of this anti-reflection film is 268Ω / □, which means that it has a practical antistatic function and a practical electromagnetic shielding function. Table 1 Example of the multilayer structure of the anti-reflection film and the thickness (nm) of each layer Example 1 Glass / PrTi03 / NiFe / PrTi03 / NiFe / PrTi03 / MgF2 | 44.9 4.9 53. 4 3. 9 20.6 84.7 Example 2 Glass / PrTiOa / NiFeCr / PrTi〇3 / NiFeCr / MgFz 54 * 1 5 6 57.6 3.3 90.3 Example 3 Glass / siNx / TiNx / SiNx / TiNx / SiNx / Si02 52.1 11 * 1 54.9 8.5 1.2 79.2 Example 4 Glass / SiNx / TiNx / SiNx / TiNx / SiOa 51.6 11.1 55, 2 8.5 79.6 Example 5 Glass / Al2〇3 / TiNx / A1z03 / TiNx / Si〇2 39.5 8.0 69.8 8.4 86.4 Example 6 Glass / Ti〇2 / TiNx / Ti02 / TiNx / SiOa 39.5 17.5 39.0 8.3 81.4 Example 7 Glass / SiN, / TiNx / SiNK / TiNx / SiNx / Si02 31.0 10.5 50 * 1 10.8 20.3 60.3 Example 8 Glass / SiNx / TlNx / SiNx / TIN, / SiOz 80, 0 9.9 67.8 6.9 100.0 Example 9 Glass / SiNx / TiNx / SiNx / TiNx / SiN * / Si02 60.0 10,0 60.0 10t0 100.0 100,0 Example 1 0 Glass / TiNx / SiNx / TiN ^ / SiNx / Si〇2 6.3 61.1 13.1 28 * 6 66.9 Example 11 Glass / PrTi03 / NiFe / PrTi03 / NiFe / PrTi03 / MgFz 31.9 6.4 61.4 3.8 28.8 100.0 Example 1 2 Glass / PrTi03 / NiFe / CrOx / NiFe / PrTi03 / MgF2 50.5 8.4 4 7.7 5.5 16.9 68.9 Example 1 3 Glass / NiFe / CrOx / NiFe / PrTi03 / MgF2 4.1 60.1 9.6 38.9 60.5 Draw Hi 88116158'pid Page 26 44 07 0ir V. Description of the invention (21) Example 3 and the glass used in Example 1 have the same optical properties and are sputtered through the magnetron Plated and coated with an antireflection film having a multilayer structure as shown in Table 1. The obtained glass article 'was examined for its transmittance and reflectance on the opposite side of the antireflection film. Based on these measured values, the visible light reflectance at the glass substrate / anti-reflective film interface is determined. Furthermore, the side opposite to the sample of the anti-reflective film is treated with anti-reflective treatment; then, the surface coated with the anti-reflective film The reflectance is measured. From these measurement results, according to JIS R 3106, the visible light transmittance Tv, the visible light reflection & r3v on the side coated with the antireflection film, and the visible light reflectance r2v at the glass substrate / antireflection film interface were obtained. The results are shown in Table 2. The visible light transmittance of the sample was 36.6%, and its value is advantageous for enhancing the contrast of the display. Because 'the surface reflectance on the side coated with the antireflection film is as low as 0.48%, Almost no image reflection occurred on the coated surface of the sample. Furthermore, 'because the reflection ratio at the glass substrate / anti-reflection film interface was as low as 0.23%, ghosting was hardly observed. The sheet of this anti-reflection film The resistance is 182Ω / □, which indicates that it has a practical antistatic function and a practical electromagnetic shielding function. Examples 4 to 10 In the same manner as in Example 3, coating Wei on a glass substrate as shown in Table 1 Samples of optical products were obtained with anti-reflection films having individual multilayer structures. The optical properties and sheet resistance of these samples are shown in Table 2. The visible light transmittance of individual samples was 35 to 40. In the range of%, its value is beneficial to enhance the contrast of the display. Individual samples are coated with anti-reflection

1 4 4 07 0 \ 4 ^ > 5. Description of the invention (22) ---- The surface reflectance of the film is as low as 1% or less, so almost no reflection occurs on the coated surface of the sample. The visible light reflectance of the individual samples at the glass substrate / = reflective film interface is as low as 1% or less, so ghost images are hardly observed. Furthermore, 'the monthly resistance of the anti-reflection film in individual samples is 208 Ω / □ or less' from the standpoint of the antistatic function and the electromagnetic shielding function, the value is quite low. ^ 2 Visible light transmittance τν (%) Visible light reflectance r3v (%) Visible light reflectance r2 v (%) at the interface Sheet resistance (Ω / □) Example 1 35.7 0.26 0. 19 112 Example 2 35.6 0.32 0.14 268 Example 3 36. 6 0. 48 0.23 182 Example 4 36.6 0.47 0.23 196 Example 5 36, 7 0.64 0.52 201 Example 6 36. 5 0. 76 0. 29 135 Example 7 34.6 0.35 0.70 164 Example 8 40. 〇.93 0.54 208 Example 9 35. 〇.62 0.68 175 Example 1 0 38. 〇0.39 0.67 185 Example 11 31. 4 0. 21 2. 61 98 Example 1 2 39.2 0. 38 1.77 330 Example 1 3 38. 9 0.69 1.25 420 [Note] The values of Tv, r3v and r2v are properties defined by the above (5) '(6),

88116158.Ptd p. 28 '4407 V. Measured values of invention descriptions (23) and (7), calculated from the light emission characteristics defined by S R 31 06'. Example 11 An antireflection film having a multilayer structure as shown in Table 1 was deposited in the same manner as in Example 1. The optical properties of the samples are shown in Table 2. The transmittance of this sample is 35 to 40%, and its value is advantageous for enhancing the contrast of the display. The surface reflectance of this sample on the side coated with the antireflection film was as low as 1% or less, so almost no image reflection occurred on the coated surface of the sample. This sample has a reflectance at the glass substrate / anti-reflective film interface as low as 3% or less, so almost no ghosting is observed. The sheet resistance of the anti-reflection film in this sample is 98 Ω / □ or less, and from the standpoint of the antistatic function and the electromagnetic shielding function, the value is quite low. Example] 2 An anti-reflection film having the same multilayer structure as in Example 11 was deposited, except that the third layer was composed of chromium oxide instead of hafnium oxide. As shown in Table 2, the obtained samples have satisfactory properties for achieving the object of the present invention. The spectral transmission characteristics of this sample are shown in FIG. 9. As shown in Fig. 9, the curve of the 'transmittance T2 does not tend to increase when the wavelength is increased, and is the same as the transmission curve shown in Fig. 8; and it is almost flat in the visible range. This is believed to be due to the fact that 'chrome oxide is more intense at longer wavelengths than at shorter wavelengths when it effectively cancels the light absorbed by the nickel-iron alloy thin film. Example A sample of an optical article having a multilayer structure as shown in Table 1 was obtained as β

88116158.ptd Page 29 44 07 0 4: V. Description of the invention (24) The sheet resistance of the anti-reflection film in this sample is 42.0 Ω / □, which is the same as that of Example 12, with its antistatic function and electromagnetic shielding function. In terms of value, it is quite low. This result goes even further-it shows that the reflection of the sample is reduced. As with the sample obtained in Example 12, the transmission curve of this sample was flat in the visible range. Comparative Examples 1 to 6 As shown in Table 3, antireflection films each having a multilayer structure were deposited on the same glass substrate as the glass substrate used in Example 1, respectively. In Comparative Examples 1 to 3, in the same manner as in Example 3, a magnetron sputtering key was used for the deposition of an anti-reflection film. In Comparative Examples 4 to 6, the same method as in Example 1 was used for the deposition of the antireflection film using vacuum evaporation. The optical properties and sheet resistance of the obtained comparative samples are shown in Table 4. The visible light transmittance of the individual comparative samples was in the range of 25 to 65%, and when used as a panel of a cathode ray tube, the displayed contrast was satisfactory. However, in the individual comparative samples, at least one of the surface reflectance on the side coated with the antireflective film and the reflectance at the glass substrate / antireflective film interface 'was 1% or more. That is, in each comparative sample, one or both of reflection and display ghosting of the fluorescent lamp occur. In other words, none of the comparative samples were free of reflections and ghosts of external light. This comparative sample was therefore found to be unsuitable for practical use.

88116158.ptd Page 30 440704 ^ V. Description of invention ¢ 25) Table 3 Comparative Example Anti-reflective film multilayer structure and thickness of each layer (nm) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Glass / Tit ^ / SiNx / Si02 21.5 41.3 40.2 Glass / SiNx / TiN Sky / SiNx / Si02 72.7 11.3 3.8 82.4 Glass / SiNx / TiNx / SiNx / TiNx / SiNx / Si02 24.9 2.1 19.8 2.1 124.2 116.1 Glass / NiFe / PrTi03 / NiFe / MgF2 1.3 39.6 3.4 110.7 Glass / Si02 / NiFe / Si02 / NiFe / Si02 / MgF2 ^ 0.2 2.9 92.4 3.0 29.5 95.8 Glass / Ti02 / NiFe / Ti02 / NiF6 / Ti02 / PrTi03 39.5 7.6 52.1 5.6 86, 3 67.6 Table 4 Comparative example Visible light transmittance Tv (%) Visible light reflectance r3v (%) Visible light reflectance r2v (%) at the interface Sheet resistance (Ω / D) Comparative example 1 37. 2 0.45 25.4 150 Comparative example 2 54. 3 4 .06 1. 43 320 Comparative Example 3 64. 2 1.56 1. 43 2100 Comparative Example 4 48. 3 4.98 2.10 101 Comparative Example 5 35. 8 1. 37 0. 34 164 Comparative Example 6 26.3 6. 30 1. 38 74 [Note] The values of Tv, r3v, and r2v are measured values of properties (5), (6), and (7) defined above, Calculated through the light emission characteristics defined by J 〖S R 3 1 0 6.

88116158.ptd Page 31 44 07 0 V. Description of the invention (26) The optical system π and the low reflection tb of the present invention. ® Γ 纟 See the inside of the enclosure has high absorption properties and contains a basic multi-layered product f glass. The anti-reflection film on the substrate, the high-refractive-index transparent dielectric film including the light-emitting film C, and the second, low-refractive-index transparent dielectric film with a high refractive index. Plate: ― a high refractive index transparent dielectric film with a fixed refractive index is interposed between the glass clay plate and the first light-absorbing thin film, and a film with a low-refractive index transparent Leyi suction 4 dielectric film. Due to this structure, light passes through the 11th layer, and then strikes the interface between the light-transmissive substrate and the anti-reflection film, showing a low reflectance at the interface. Therefore, by arranging any optical product of the present invention on the display surface of a cathode ray tube, a high-contrast display image can be obtained without causing ghosting. When the light-absorbing film is a single component or a thin layer of two or more components, the component is composed of titanium, chromium, tungsten, molybdenum, iron, niobium, buttons, hafnium, nickel, nickel-iron alloy, and stainless steel. It is selected from the group of metals; it is conducive to enhancing the light absorption property of the contrast image displayed by the cathode ray tube, and can be imparted to the optical product. In addition to this, due to the conductivity of these light-absorbing films, antistatic properties and electromagnetic shielding properties can also be imparted. When the light-absorbing film is an element or a film of two or more elements, the element is a metal nitride group composed of titanium nitride, chromium nitride, nitride nitride, nitride nitride, and nitride button. It can be given to optical products, which can be used to enhance the contrast of the light-absorbing properties of the display image presented by the cathode-ray tube. In addition, because these light-absorbing thin

88'16l58.ptd Page 32 4 4 07043 1 1 — — 5. Explanation of the invention (27) The conductivity of the film, its antistatic properties and electromagnetic shielding properties can also be assigned. When used in the present invention, the light transmission When the substrate is composed of colored glass containing color components, ghosting can be avoided more effectively. The display area in the cathode ray tube is covered with any of the optical products of the present invention, does not reflect external light, and can present a high-contrast image without causing ghosting. Although the present invention has been described in detail with reference to specific specific examples; those skilled in the art will all know that various changes and modifications can be made without departing from the spirit and scope of the invention.

88116158.ptd Page 33

Claims (1)

6. Patent application scope I An optical article with an anti-reflection coating, comprising a light-transmissive substrate with a refractive index of 1.4 to 1.7, and an anti-reflection film composed of overlapping layers on the light-transmissive substrate in the following order Formation: a light-absorbing thin film is the first layer; a transparent dielectric film with a refractive index of 1.6 to 2.4 is a second layer; a light-absorbing film is a third layer; a transparent dielectric film with a refractive index of 1.6 to 2.4 is a fourth layer , And a transparent dielectric film having a refractive index of 1.3 to 1.5 is a fifth layer. 2. The optical products with anti-reflection coatings in which the scope of the patent application is No. 1 'wherein' is a transparent dielectric thin layer of the second and fourth layers, respectively, with a thickness of 30 to 80 nm, and the fifth layer is The thickness of the transparent dielectric film is 60 to 100 nm. 3. For example, the optical products with anti-reflection coating in item 1 of the patent application scope, wherein the light-absorbing films are each a film containing at least one metal, which is composed of titanium, chromium, copper, molybdenum, iron, sharp, and , Feed, record, nickel-iron alloy and stainless steel. 4. For example, the optical product with an anti-reflection coating in item 3 of the patent application range, wherein the individual thickness of the light-absorbing film is 5 to 8 nm. 5. The optical product with an anti-reflection coating according to item 1 of the patent application, wherein the transparent dielectric film with a refractive index of 1.6 to 2.4 is at least one layer of a chromium oxide film. 6. If the optical product with anti-reflection coating in item 1 of the patent application 'wherein' the light-absorbing film is a film containing at least one metal nitride, the metal nitride is composed of titanium nitride, chromium nitride, nitride It is selected from the group consisting of wrong, hafnium nitride, and nitride button. 7 An optical system with an anti-reflection coating, such as the scope of patent application No. 6 Page 34 88116158, ptd 6. Scope of Patent Application Product ‘Where’ the individual light absorbing film is 3 to 6 nm thick. 8. An optical article having an anti-reflection coating, comprising a light-transmissive substrate having a refractive index of 1 to 4 and 1.7, and an anti-reflection film composed of an overlapping layer, and the light-transmissive substrate is formed in the following order: Formed on: a transparent dielectric film with a refractive index of .6 to 2.4 is the first layer, a light absorbing film is the second layer, a transparent dielectric film with a refractive index of 1.6 to 2.4 is the third layer, and a light absorbing film It is the fourth layer, and a transparent dielectric film with a refractive index of 1.35 to 1.5 is the fifth layer. 9. For example, an optical article with an anti-reflection coating according to item 8 of the scope of patent application, which further has a transparent dielectric film having a refractive index of 6 to 2.4 as the sixth layer, which is interposed between light absorption as the fourth layer Between the film and the transparent dielectric film as the fifth layer. 10. The optical article with an anti-reflection coating according to item 8 of the scope of patent application, wherein the individual thicknesses of the transparent dielectric films as the first and third layers are 30 to 80 nm, respectively, and the fifth layer is transparent as the transparent layer. The dielectric film is 60 to 100 nm. 'And Π. The optical product with an anti-reflection coating according to item 9 of the scope of patent application, wherein the thickness of the transparent dielectric film as the sixth layer is not 100 nm. 1 2. The optical article with an anti-reflection coating according to item 8 of the scope of patent application, wherein each of the light-absorbing films is a film containing at least one metal, which is made of titanium, chromium, zirconium, molybdenum, iron, niobium, Selected from the group consisting of tantalum, hafnium, nickel, nickel-iron hafnium alloy and stainless steel. 1) According to claim 12 of the scope of patent application, a light product with an anti-reflection coating, wherein the individual thickness of the light-absorbing film is 3 to 6ηm. , . 1, 4. The transparent dielectric thin film with an anti-reflection coating and an intermediate refractive index i. 6 to 2.4 according to item 2 of the patent application scope, at least one of which is a chromium oxide film. 1 5. The optical article with an anti-reflection coating according to item 8 of the scope of the patent application, wherein the light absorbing film is a film containing at least one metal nitride, and the metal nitride is composed of titanium nitride and chromium nitride. Hafnium nitride, nitride nitride, and tantalum nitride are selected from the group consisting of: 16. The optical product with an anti-reflection coating according to item 15 of the scope of patent application, wherein the thickness of each of the light-absorbing films is 5 to δ δ. 17. An optical article having an anti-reflection coating as claimed in item 1 or 8 of the patent application scope, wherein the 'light-transmissive substrate is a glass substrate. 8. The optical article with an anti-reflection coating according to item 17 of the scope of patent application, wherein the light-transmittable substrate is made of glass for a cathode ray tube. A few degrees of light of the reflective coating. Among them, the light-transmitting glass substrate contains a colored component ^ which has the property of absorbing light. Therefore, 20. A type of cathode ray tube, which uses an optical article having an anti-reflection coating as described in the scope of patent application. Or 8 88116158.ptd Page 36